CN110302836B - Preparation method and application of graphene oxide supported diimine coordination palladium - Google Patents

Preparation method and application of graphene oxide supported diimine coordination palladium Download PDF

Info

Publication number
CN110302836B
CN110302836B CN201910540152.3A CN201910540152A CN110302836B CN 110302836 B CN110302836 B CN 110302836B CN 201910540152 A CN201910540152 A CN 201910540152A CN 110302836 B CN110302836 B CN 110302836B
Authority
CN
China
Prior art keywords
diimine
graphene oxide
palladium
oxide supported
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910540152.3A
Other languages
Chinese (zh)
Other versions
CN110302836A (en
Inventor
李田
孙云龙
刘丰收
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Pharmaceutical University
Original Assignee
Guangdong Pharmaceutical University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong Pharmaceutical University filed Critical Guangdong Pharmaceutical University
Priority to CN201910540152.3A priority Critical patent/CN110302836B/en
Publication of CN110302836A publication Critical patent/CN110302836A/en
Application granted granted Critical
Publication of CN110302836B publication Critical patent/CN110302836B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/06—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
    • C07C251/08—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton being acyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D277/24—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D277/30—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C07F15/0066—Palladium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a preparation method and application of graphene oxide supported diimine coordination palladium. The graphene oxide supported diimine coordination palladium is prepared by the following preparation method: 1) reacting diimine with aldehyde group with a silane coupling agent to obtain a silane coupling agent modified diimine ligand; 2) reacting silane coupling agent modified diimine ligand with graphene oxide to obtain graphene oxide loaded diimine ligand; 3) reacting graphene oxide supported diimine ligand with palladium salt. Simultaneously, the application of the graphene oxide supported diimine coordination palladium as a catalyst in organic synthesis reaction is also disclosed. The catalyst obtained by the invention can efficiently catalyze the Suzuki coupling reaction and the C-H direct arylation reaction under the condition of low consumption; the ligand is firmly loaded on the graphene in a Schiff base combination mode, so that the catalyst can be recycled for multiple times, and the method has good application and popularization prospects.

Description

Preparation method and application of graphene oxide supported diimine coordination palladium
Technical Field
The invention belongs to the technical field of catalytic materials, and particularly relates to a preparation method and application of graphene oxide loaded diimine coordination palladium.
Background
The palladium is located in the second transition period, and the moderate atomic radius and the unique electronic arrangement of the palladium form the stability of the palladium complex and the diversity of catalytic performances, particularly the outstanding catalytic activity on reactions involving carbon-carbon bond formation. At first, homogeneous catalysts such as palladium salt, palladium complex and the like are commonly used, and have the advantages of good dispersibility, high catalytic efficiency, excellent selectivity and the like, but the catalysts are difficult to separate because the catalysts and a reaction system react in the same phase, expensive palladium is difficult to recycle, and residues cause pollution to products. Thus, the preparation of supported palladium catalysts which can be separated by simple filtration, both from an economic and environmental point of view, hasOf great significance. At present, a plurality of carriers such as carbon materials, metal oxides, polymers and the like are applied to the preparation of supported palladium catalysts, the obtained catalysts can be recycled for a plurality of times under the mild condition of no water and no oxygen, and catalyze various coupling reactions such as Suzuki and the like, and the supported palladium catalysts have wider adaptability and application prospects in the industries such as medicine, chemical engineering and the like (Pal N, Bhaumik A. mesoporous materials: versatic support in heterologous catalysis for liquid phase catalytic transformation. RSC Advances.2015,5: 363 24391; Baran T, Sargin I, Kaya M,
Figure BDA0002102294210000011
A,Ceter T.Design and application of sporopollenin microcapsule supported palladium catalyst:remarkably high turnover frequency and reusability in catalysis of biaryls.Journal of Colloid and Interface Science.2017,486:194–203)。
at present, most of supported palladium catalysts are prepared by a simple impregnation method or an ion exchange method, and Pd is adsorbed by physics or under the action of static electricity2+And carrying out loading. Due to the support and Pd2+Has weak interaction force and generates Pd with a reducing substrate when catalyzing Suzuki-Miyaura and the like0Easily aggregated into clusters, forming pd black, and suffering from catalytic cycle fatality (Lichtenegger G J, Maier M, Hackl M, Khinast J G,
Figure BDA0002102294210000012
w, Griesser T, Phani Kumar V S, Gruber-Woeller H, Desmopandre P A. Suzuki-Miyaura coupled interactions using novel metal oxide supported ionic palladium catalysts. journal of Molecular Catalysis A: chemical.2017,426: 39-51). In addition, the catalyst directly supporting palladium ions or zero-valent palladium has another disadvantage that the catalyst cannot be combined with a reaction substrate through coordination to activate the reaction substrate, the reaction activation energy is reduced, a product cannot be formed through coordination and configuration change, the catalytic cycle is rapidly completed, and the high activity and selectivity of the homogeneous coordination palladium catalyst under the same dosage are difficult to achieve. For example, Pd supported2+Or Pd0P-chlorobenzene as catalystThe catalytic activity of the coupling reaction of the carbene complex palladium homogeneous catalyst and phenylboronic acid is very low, but the yield (Lan X B, Chen F M, Ma B, Shen D S, Liu F S. Pd-PEPSI complex contacting bulk [ (1,2-Di- (tert-butyl)) can reach 98% only by adding the carbene complex palladium homogeneous catalyst in an amount of 0.05-0.1 mol%](DtBu-An)on N-heterocarbene backbones:highly efficient for Suzuki-Miyaura cross-coupling under aerobic conditions.Organometallics.2016,35:3852-3860)。
The introduction of complex palladium on a support has been a promising approach, but is also difficult. Because the coordination preparation process is complex, the in-situ synthesis on the carrier is difficult, and the introduction can be carried out only on the surface of the carrier containing a specific functional group. The polymer has low skeleton density, controllable chemical and physical properties and rich surface functional groups, can be modified and modified, can be well combined with a ligand, can further adjust the structure of the carrier by a flexible and various polymerization method, is very easy to be uniformly mixed and separated with reaction liquid when being used as the carrier of the catalyst, has the advantage of unique thickness, and is an ideal coordination palladium carrier material. However, the heat resistance is relatively poor due to the characteristics of the polymer itself, for example, since the Bergbreiter uses polyisobutylene as the carrier to support the complex palladium, decomposition of the carrier occurs when the carrier is heated at 60 ℃ for 3 hours (Bergbreiter D E, Su H L, Koizumi H, Tian J. polyisobutylene-supported N-heterocyclic carbon palladium catalysts. journal of Organometallic chemistry.2011,696: 1272-. Therefore, many researchers have attempted to support the complex palladium on a more stable performance silicon support. Martininez and the like load Pd-NHC on the surface of dialkoxysilane modified silica, the amount of palladium loading can reach 1.7-2.6 wt%, but palladium black appears after repeated recycling, which indicates that palladium is separated from the ligand and is agglomerated (Martininez A, Krinsky J L,
Figure BDA0002102294210000021
i, Castill Lo n S, Loponov K, Lapkin A, Godard C, Claver C. hybridization of Pd-NHC complexes on to a silicon support and the same application in Suzuki-Miyaura linking unit batch and connecting flows conditions, catalysis Science and technology.2015,5: 310-. Is especially suitable for the treatment of diabetesThe reason for this is that the silicon carrier does not act strongly with the coordinated palladium and it is difficult to achieve tight binding. Schlem's initiative (Schlem's initiative, preparation and catalytic properties of graphene oxide-supported bisimine palladium, nickel and nickel/palladium bimetallic catalyst self-assembled membrane, Zheng Zhou university Master thesis, 2017) synthesized bisimine ligand containing triethoxysilane at the terminal, PNB was grafted to the graphene oxide surface through silanization reaction, and palladium ions were supported for use as a Suzuki reaction catalyst. However, the bis-diimine ligand introduced on the catalyst only provides an active metal coordination site, and cannot well protect the active metal center of Pd (0), so that the catalyst is easy to deactivate.
Therefore, the establishment of firmer combination with the coordination palladium with proper steric hindrance and electronic effect on the surface of the stable carrier becomes the key for obtaining the high-efficiency supported coordination palladium catalyst.
Disclosure of Invention
In order to overcome the problems that a common heterogeneous palladium catalyst is easy to aggregate and lose efficacy, the catalytic activity is not high, palladium of a homogeneous coordination palladium catalyst is easy to lose, and the product is difficult to process after, the invention aims to provide graphene oxide supported diimine coordination palladium, and aims to provide a preparation method of the graphene oxide supported diimine coordination palladium and an application of the graphene oxide supported diimine coordination palladium.
The technical scheme adopted by the invention is as follows:
the invention provides a preparation method of graphene oxide supported diimine coordination palladium, which comprises the following steps:
1) reacting diimine with aldehyde group with a silane coupling agent to obtain a silane coupling agent modified diimine ligand;
wherein, the structure of the diimine with aldehyde group is shown as formula (1):
Figure BDA0002102294210000031
2) reacting silane coupling agent modified diimine ligand with graphene oxide to obtain graphene oxide loaded diimine ligand;
3) reacting the graphene oxide supported diimine ligand with palladium salt to obtain graphene oxide supported diimine coordination palladium.
In the preparation method of the graphene oxide supported diimine ligand palladium, in step 1), diimine with aldehyde groups and a silane coupling agent are combined in a Schiff base manner to obtain a silane coupling agent modified diimine ligand; silane coupling agent modified diimine ligands, i.e., diimine ligands grafted with alkoxysilane groups.
Preferably, the preparation method of graphene oxide supported diimine coordination palladium comprises the step 1) of specifically mixing diimine with aldehyde groups and a silane coupling agent in a molar ratio of 1: (2-5) mixing the mixture in an organic solvent, and reacting to obtain the silane coupling agent modified diimine ligand.
Preferably, in step 1) of the preparation method of graphene oxide supported diimine coordination palladium, the molar ratio of diimine with aldehyde groups to silane coupling agent is 1: (2-3); further preferably, the molar ratio of the diimine with aldehyde groups to the silane coupling agent is 1: (2-2.4).
Preferably, in step 1) of the preparation method of graphene oxide supported diimine coordination palladium, the preparation method of diimine with aldehyde groups is as follows: performing halogenation reaction on the 2, 6-diisopropylaniline to obtain halogenated 2, 6-diisopropylaniline; reacting halogenated 2, 6-diisopropylaniline with glyoxal to obtain a diimine compound; reacting the diimine compound with 4-formylphenylboronic acid to obtain diimine with aldehyde group.
Wherein, the structure of the halogenated 2, 6-diisopropyl aniline is shown as the formula (2):
Figure BDA0002102294210000032
in formula (2), X represents halogen, and X is preferably Cl, Br or I; further preferably, X is I.
The structure of the diimine compound is shown as the formula (3):
Figure BDA0002102294210000041
in the formula (3), X represents halogenX is preferably Cl, Br or I; further preferably, X is I.
Further, in the preparation method of the diimine with aldehyde group, the halogenation reaction is specifically to react 2, 6-diisopropylaniline with iodine simple substance to obtain 4-iodine-2, 6-diisopropylaniline. Wherein, the solvent of the halogenation reaction is an alkane solvent, and cyclohexane is preferred; the catalyst of the halogenation reaction is alkali or alkali carbonate, preferably sodium carbonate; the molar ratio of the 2, 6-diisopropylaniline to the iodine simple substance is 1: (1-2), and the preferable molar ratio is 1: (1-1.2); the temperature of the halogenation reaction is room temperature; the time of the halogenation reaction is 8h to 15h, and the preferable reaction time is 12 h.
Further, in the preparation method of the diimine with aldehyde group, halogenated 2, 6-diisopropylaniline reacts with glyoxal, and the solvent for the reaction is an alcohol solvent, preferably methanol; the reaction is carried out for 10 to 15 hours at room temperature, and the preferable reaction time is 12 hours; the molar ratio of the halogenated 2, 6-diisopropylaniline to glyoxal is (2-3): 1, the preferable molar ratio is (2-2.2): 1.
further, in the preparation method of the diimine with aldehyde group, the diimine compound reacts with 4-formylphenylboronic acid, and the solvent for the reaction is an alcohol solvent, preferably ethanol; the catalyst for the reaction is preferably Pd-PEPSI-IPr; the dosage of the catalyst for the reaction is 0.5 mmol-1.5 mmol, preferably 1 mmol; the reaction is carried out in a protective atmosphere, wherein the protective atmosphere is nitrogen or inert gas atmosphere; the reaction temperature is 80-95 ℃, and preferably 90 ℃; the molar ratio of the diimine compound to 4-formylphenylboronic acid is 1: (2-3), and the preferable molar ratio is 1: (2-2.2).
Preferably, in the preparation method of graphene oxide supported diimine coordination palladium, in step 1), the organic solvent is an aromatic hydrocarbon solvent; further preferably, the organic solvent is selected from one or two of toluene and xylene.
Preferably, the preparation method of the graphene oxide supported diimine coordination palladium in step 1) further comprises adding a catalyst to participate in the reaction, wherein the catalyst is an acid catalyst, such as glacial acetic acid.
Preferably, in the preparation method of the graphene oxide supported diimine coordination palladium, in the step 1), the reaction temperature is 80-120 ℃; further preferably, the reaction temperature is 90 ℃ to 110 ℃.
Preferably, in the preparation method of the graphene oxide supported diimine coordination palladium, in the step 1), the reaction time is 8-72 h; more preferably, the reaction time is 10 to 48 hours.
Preferably, in step 1) of the preparation method of graphene oxide supported diimine coordination palladium, the reaction is carried out in a protective atmosphere; the protective atmosphere is nitrogen or inert gas atmosphere; further preferably, the protective atmosphere is a nitrogen, argon or neon atmosphere.
Preferably, in step 1) of the preparation method of graphene oxide supported diimine coordination palladium, the general formula of the silane coupling agent is NH2(CH2)nSi(OR1)3Wherein n is 1 to 6, R1Is methyl or ethyl; more preferably, the silane coupling agent is 3-Aminopropyltriethoxysilane (APTES).
Preferably, in step 1) of the preparation method of graphene oxide supported diimine coordination palladium, a silane coupling agent modified diimine ligand has a structure shown in formula (4):
Figure BDA0002102294210000051
in formula (4), n is 1,2, 3, 4, 5 or 6; r1is-CH3or-C2H5。
Further, when the silane coupling agent is 3-aminopropyltriethoxysilane, the silane coupling agent modified diimine ligand is obtained, and the structure of the diimine ligand is shown in the formula (5):
Figure BDA0002102294210000052
preferably, the step 2) of the preparation method of graphene oxide supported diimine coordination palladium is specifically as follows: mixing a silane coupling agent modified diimine ligand and graphene oxide in a mass ratio of (1-4): 1 in an organic solvent, and reacting to obtain the graphene oxide supported diimine ligand.
Preferably, in step 2) of the preparation method of graphene oxide supported diimine coordination palladium, the mass ratio of the silane coupling agent modified diimine ligand to graphene oxide is (1.5-2.6): 1.
preferably, in step 2) of the preparation method of graphene oxide supported diimine coordination palladium, the structure of the graphene oxide supported diimine ligand is shown as formula (6):
Figure BDA0002102294210000053
in formula (6), GO represents graphene oxide.
Preferably, in step 2) of the preparation method of graphene oxide supported diimine coordination palladium, the preparation method of graphene oxide includes the following steps:
s1: adding graphite powder into concentrated sulfuric acid under an ice bath condition, and stirring for 0.5-1.5 h;
s2: continuously adding potassium permanganate to react, controlling the reaction temperature below 20 ℃ and the reaction time to be 0.5-1.5 h;
s3: continuously stirring and reacting for 2.5-3.5 h in a water bath at the temperature of 30-40 ℃; adding deionized water, controlling the reaction temperature to be 92-98 ℃, and stirring for 10-20 min; then adding water and stopping reaction;
s4: and continuously adding hydrogen peroxide, stopping when the solution just turns yellow, changing the solution from brown black to bright yellow, pouring out supernatant, and washing the product to obtain the graphene oxide.
Preferably, in the preparation method of the graphene oxide, the use amount ratio of the graphite powder, the concentrated sulfuric acid, the potassium permanganate, the deionized water, the water and the hydrogen peroxide is 1 g: (20-30) mL: (2-4) g: (30-60) mL: (100-200) mL: (4-6) mL.
Preferably, in the preparation method of the graphene oxide, H is added into hydrogen peroxide2O2The mass concentration of the active carbon is 25 to 35 percent; further preferably, H in hydrogen peroxide2O2The mass concentration of (2) is 30%.
Preferably, in step 2) of the preparation method of graphene oxide supported diimine coordination palladium, the organic solvent is selected from at least one of alcohols, ketones, esters, ethers and amide solvents; further preferably, the organic solvent is selected from one or more of ethanol, isopropanol, acetone, ethyl acetate, diethyl ether and N, N-dimethylformamide; still further preferably, the organic solvent is selected from ethanol or isopropanol.
Preferably, in the step 2) of the preparation method of graphene oxide supported diimine coordination palladium, the reaction temperature is 60-100 ℃; further preferably, the reaction temperature is 70 ℃ to 90 ℃.
Preferably, in the step 2) of the preparation method of graphene oxide supported diimine coordination palladium, the reaction time is 6-24 hours; more preferably, the reaction time is 8 to 15 hours.
Preferably, in step 2) of the preparation method of graphene oxide supported diimine coordination palladium, the reaction is carried out in a protective atmosphere; the protective atmosphere is nitrogen or inert gas atmosphere; further preferably, the protective atmosphere is a nitrogen, argon or neon atmosphere.
Preferably, the step 3) of the preparation method of graphene oxide supported diimine coordination palladium specifically is: carrying out mass ratio (1-10) of a graphene oxide supported diimine ligand to palladium salt: 1, mixing the mixture in an organic solvent, and reacting to obtain the graphene oxide supported diimine coordination palladium.
Preferably, in step 3) of the preparation method of graphene oxide supported diimine coordination palladium, the mass ratio of the graphene oxide supported diimine ligand to palladium salt is (2-4): 1.
preferably, in step 3) of the preparation method of graphene oxide supported diimine coordination palladium, the palladium salt is selected from a divalent palladium salt or a zero-valent palladium salt; further preferably, the palladium salt is at least one selected from palladium chloride, palladium acetate, tris (dibenzylideneacetone) dipalladium and bis (tri-tert-butylphosphino) palladium; still more preferably, the palladium salt is palladium chloride.
Preferably, in step 3) of the preparation method of graphene oxide supported diimine coordination palladium, the organic solvent is selected from at least one of alcohols, ketones, esters, ethers and amide solvents; further preferably, the organic solvent is selected from one or more of ethanol, isopropanol, acetone, ethyl acetate, diethyl ether and N, N-dimethylformamide; still more preferably, the organic solvent is N, N-dimethylformamide.
Preferably, in the step 3) of the preparation method of graphene oxide supported diimine coordination palladium, the reaction temperature is 60-100 ℃; further preferably, the reaction temperature is 70 ℃ to 90 ℃.
Preferably, in the step 3) of the preparation method of graphene oxide supported diimine coordination palladium, the reaction time is 6-24 hours; more preferably, the reaction time is 8 to 15 hours.
Preferably, in step 3) of the preparation method of graphene oxide supported diimine coordination palladium, the reaction is carried out in a protective atmosphere; the protective atmosphere is nitrogen or inert gas atmosphere; further preferably, the protective atmosphere is a nitrogen, argon or neon atmosphere.
Preferably, in step 3) of the preparation method of graphene oxide supported diimine coordination palladium, when the palladium salt is palladium chloride, the structure of the obtained graphene oxide supported diimine coordination palladium is shown as formula (7):
Figure BDA0002102294210000071
in formula (7), GO represents graphene oxide.
The invention provides graphene oxide supported diimine coordination palladium, which is prepared by the method.
The structure of the graphene oxide supported diimine coordination palladium is shown as a formula (7).
The invention also provides application of the graphene oxide supported diimine coordination palladium as a catalyst in organic synthesis reaction.
Preferably, in application, the organic synthesis reaction is a Suzuki reaction or a C-H activation reaction.
The invention has the beneficial effects that:
the invention designs diimine palladium with glyoxal as a skeleton structure, which is loaded on graphene oxide in a Schiff base combination mode; the diimine ligand of the glyoxal skeleton has small position resistance, can be embedded with graphene as much as possible, the electronic effect and the steric effect of isopropyl with proper steric hindrance of an N-aryl part greatly improve the coupling reaction yield, and the obtained catalyst can catalyze the Suzuki coupling reaction and the C-H direct arylation reaction with high efficiency under the condition that the using amount is only 0.047% mmol; the ligand is firmly loaded on the graphene in a Schiff base combination mode, so that the catalyst can be recycled for multiple times.
The graphene oxide supported diimine coordination palladium catalyst overcomes the defects that a common heterogeneous palladium catalyst is easy to aggregate and lose efficacy, the catalytic activity is not high, palladium of the homogeneous coordination palladium catalyst is easy to run off, and the product is difficult to post-treat, is very convenient to use, and has good application and popularization prospects.
Compared with the prior art, the invention has the following advantages:
the palladium loading amount of the graphene oxide supported palladium (Pd @ GO) catalyst is only 0.53%, and the palladium loading amount of the graphene oxide supported diimine coordination palladium (Pd-DI @ GO) catalyst can reach 5.04%. The isopropyl introduced by the N-aryl part has an electronic effect and provides proper steric hindrance, and in the process of Suzuki coupling reaction and C-H direct arylation reaction, the protective effect on the active metal center Pd (0) is stronger, and the Pd (0) can not be poisoned as far as possible, so that the reaction yield is greatly improved, and the universality is better. The ligand is firmly combined on the surface of the graphene oxide through Schiff base, so that the catalyst can be recycled for many times. When the Pd-DI @ GO catalyst is used for catalyzing Suzuki reaction, the yield is 98% when the dosage is 1mg, and the catalyst can be recycled for 4 times, while when the dosage is 5mg, the yield is 8%, the catalyst can be used only for 1 time, and the second activity is too low.
Drawings
FIG. 1 is a schematic diagram of a preparation process of graphene oxide supported diimine coordination palladium;
FIG. 2 is a diya having an aldehyde groupOf amines1H NMR spectrum;
FIG. 3 is a diagram of diimines with aldehyde groups13C NMR spectrum;
FIG. 4 is an XPS spectrum of graphene oxide supported diimine coordination palladium;
FIG. 5 shows Pd 3d in graphene oxide supported diimine coordination palladium3/2And 3d5/2XPS spectra of (a);
fig. 6 is an XPS spectrum of N1 s in graphene oxide supported diimine coordination palladium.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials used in the examples are, unless otherwise specified, commercially available from conventional sources.
Examples
Preparation of graphene oxide
23mL of concentrated sulfuric acid (98 wt% H)2SO4) And cooling in an ice bath, ensuring that the temperature of the system is lower than 5 ℃, adding 1g of graphite powder while stirring, and continuing stirring for 1 h. After mixing well, 3g KMnO was slowly added4In order to prevent the liquid from splashing, the reaction temperature is controlled below 20 ℃ (the stirring and dripping speed is slow and uniform), and the reaction is carried out for 1 hour. And (3) putting the beaker into a constant-temperature water bath at 35 ℃, uniformly stirring, and reacting for 3 hours. 46mL of deionized water was added, the reaction temperature was controlled (slow, wall, exothermic) to 95 deg.C, stirring was continued for 15min, and then 140mL of water was added to stop the reaction. 5mL of hydrogen peroxide (30 wt% H)2O2) Adding into the reaction system (first rapid and then slow), stopping when the solution turns yellow, changing the solution from brown black to bright yellow, pouring out the supernatant, washing with 2 wt% HCl solution for 2 times for purification, and washing with water for three times. Centrifuging the graphene oxide, pouring out supernatant, dropwise adding some water, and continuously centrifuging until the pH value of the supernatant is 5. And carrying out ultrasonic treatment on the graphene oxide for 30-60 min at the temperature of below 35 ℃. After 30min, the ultrasonic treatment is suspended for a while and is carried out for 30min again, the mixture is poured into a culture dish and put into a freeze-drying box (the thickness is 5mm, and the freeze-drying box is stored under the conditions of low temperature, drying and light shielding). 0.1g of graphene oxide is put into a beaker, 200mL of water is added, and the mixture is subjected to ultrasonic treatment for 1 hour to obtain a brown yellow transparent solution.
Preparation of diimine with aldehyde group
Fig. 1 is a schematic flow chart of the preparation process of the graphene oxide supported diimine coordination palladium. The preparation method of this example is described below with reference to FIG. 1:
2, 6-diisopropylaniline (50mmol), iodine (55mmol) and saturated Na were added2CO3(14mL) the solution was stirred in cyclohexane (50mL) at room temperature for 12h to give 4-iodo-2, 6-diisopropylaniline (Compound 1a in FIG. 1); 4-iodo-2, 6-diisopropylaniline (21mmol) and glyoxal (10mmol) in 50mL methanol at room temperature for 12h to give diimine (compound 2a in FIG. 1); and then using ethanol (40mL) as a solvent, and reacting the diimine (10mmol), 4-formylphenylboronic acid (20.5mmol) and Pd-PEPSI-IPr (1 mmol%) at 90 ℃ under the protection of nitrogen to generate diimine with aldehyde groups (compound 3a in figure 1, namely the compound shown in the formula 1).
FIG. 2 is a diagram of diimines with aldehyde groups1H NMR spectrum.1H NMR(400MHz,CDCl3)δ10.08(s,CHO-H,2H),8.17(s,NH2-H,2H),7.98(d,J＝8.2Hz,Ar-H,4H),7.79(d,J＝8.2Hz,Ar-H,4H),7.46(s,Ar-H,4H),3.02(dd,J＝13.7,6.9Hz,Ar-H,4H),1.29(d,J＝6.9Hz,CH3-H,24H)。13C NMR(101MHz,CDCl3)δ192.0,169.7,163.1,150.4,148.4,147.59,137.6,136.6,135.0,130.3,127.5,122.5,77.3,77.0,76.7,28.3,23.4。
FIG. 3 is a diagram of diimines with aldehyde groups13C NMR spectrum.13C NMR(101MHz,CDCl3) δ 192.0,169.7,163.1,150.4,148.4,147.59,137.6,136.6,135.0,130.3,127.5,122.5,77.3,77.0,76.7,28.3, 23.4. Preparation of graphene oxide supported diimine coordination palladium catalyst
Adding 1mmol of diimine with aldehyde group into a 100mL round bottom flask, adding 2.1mmol of 3-Aminopropyltriethoxysilane (APTES) and 8mL of glacial acetic acid, using toluene (40mL) as solvent, and adding N2Protection, reaction at 100 ℃ for 12h, and repeatedly washing the product with ethanol and dichloromethane until the washing liquid is clear to obtain the product (the compound 4a in figure 1, namely the compound of the formula 5).
0.5mmol of compound 4a and 0.25g of graphene oxide were added100mL round bottom flask, ethanol (40mL) as solvent, N2Protecting, reacting at 80 ℃ for 12h, repeatedly washing the product with ethanol and dichloromethane after the reaction is finished until the washing liquid is clear. And drying at 60 ℃ to obtain the graphene oxide supported diimine ligand (compound 5a in figure 1, namely the compound shown in the formula 6).
0.6mmol of PdCl is taken2Adding the mixture into a round-bottom flask, adding 0.34g of graphene oxide supported diimine ligand into the round-bottom flask, taking DMF (40mL) as a reagent, and adding N2Protecting, reacting at 80 ℃ for 12h, repeatedly washing the product with DMF and dichloromethane after the reaction is finished until the washing liquid is clear. Drying at 60 ℃ to obtain a target product Pd-DI @ GO (a compound C1 in figure 1, namely the compound of the formula 7).
The XPS spectrum of the graphene oxide supported diimine coordination palladium in the example is shown in figure 4, Pd 3d3/2And 3d5/2The XPS spectrum of (A) is shown in FIG. 5, and the XPS spectrum of N1 s is shown in FIG. 6. The XPS test results shown in fig. 4-6 show that the graphene oxide supported diimine coordination palladium prepared in this example has peaks corresponding to divalent palladium at 342.4eV and 337.0eV, and the N element peak at 399.3eV further confirms the coordination between the nitrogen element and the palladium element.
Comparative example
Preparation of graphene oxide supported metal palladium (Pd @ GO): taking graphene oxide and PdCl2Adding into a round bottom flask with a branch mouth, taking DMF as a reagent, and adding N2Protecting, reacting for 12h at 70 ℃, repeatedly washing the product with DMF and dichloromethane after the reaction is finished until the washing liquid is clear. Drying at 60 ℃ to obtain a target product Pd @ GO.
Application example 1
The application comparison of the graphene oxide supported diimine coordination palladium catalyst (Pd-DI @ GO obtained in the example) and the graphene oxide supported palladium catalyst (Pd @ GO obtained in the comparative example) is carried out:
Pd-DI @ GO and Pd @ GO are respectively used as catalysts for Suzuki reaction, and the reaction is as follows: 4-bromobenzaldehyde (1mmol), 2-methoxyphenylboronic acid (1.5mmol), K2CO3(2mmol), catalyst (5mg) was reacted in absolute ethanol at 65 ℃ for 2 h. The specific dosage of each raw material is4-bromobenzaldehyde 0.185g, 2-methoxyphenylboronic acid 0.229g, K2CO30.276g of Pd-DI @ GO or Pd @ GO 0.005g and 5mL of absolute ethyl alcohol.
The palladium loading of Pd-DI @ GO and Pd @ GO and the palladium content and yield data in the reaction liquid for catalyzing the Suzuki reaction are shown in Table 1. The palladium loading amount was measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES).
TABLE 1 Pd-DI @ GO and Pd @ GO palladium loading and palladium content and yield data in reaction solution for catalyzing Suzuki reaction
Catalyst sample Amount of Palladium on the Palladium (wt%) Palladium content (ppm) in the reaction solution Yield (%)
Pd-DI@GO 5.04 <1 99
Pd@GO 0.53 <1 8
As can be seen from Table 1, the amount of palladium supported by the catalyst prepared by the method of the present invention is greatly improved compared with that of the catalyst prepared by graphene oxide supported by palladium, the yield is also significantly increased, the palladium content in the reaction solution is very low, and the palladium loading in the catalyst is very firm.
Application example 2
The Pd-DI @ GO catalyst prepared by the method is used for catalyzing Suzuki coupling reaction of different substrates. The reaction can be seen in the following equation:
Figure BDA0002102294210000101
wherein the reaction conditions are as follows: ArBr (1.0mmol), ArB (OH)2(1.5mmol)，Pd-DI@GO(0.047％mmol-0.235％mmol)，K2CO3(2.0mmol), EtOH (4mL), 65 ℃, 2h, air atmosphere.
The results corresponding to the above equations and the resulting yield data are shown in Table 2.
Table 2 test of catalytic performance of graphene oxide supported diimine coordination palladium catalyst on Suzuki reaction
Serial number R1 R2 Yield (%)
1 4-CHO H 99
2 4-CHO 2-CH3 99
3 4-CHO 4-CH3 99
4 4-CHO 2,-OCH3 91
5 2-CHO H 91
6 4-COCH3 H 99
7 4-COOC2H5 H 89
8 4-COCH 3 3,5-CH3 99
9 4-COCH3 2-OCH3 99
10 2,6-CH3 H 81
11 4-Cl H 91
12 4-CH3 H 99
13 4-CH3 4-CH3 93
14 4-H H 99
15 2-CH3 H 84
16 4-NO2 H 98
17 4-CN H 99
18 4-CN 2-OCH3 81
19 2-CN 4-OCH3 92
20 2-OCH3 2-OCH3 52
As can be seen from the results in Table 2, the activity of Pd-DI @ GO is greatly improved relative to Pd @ GO, for example, the yield of the Pd-DI @ GO reaction with catalytic number 1 is 99%, while the Pd @ GO is only 15%; the yield of the Pd-DI @ GO catalytic No. 5 reaction is 99%, and the Pd @ GO catalytic amount is only 8%; the yield of the Pd-DI @ GO catalytic No. 12 reaction is 99%, while the Pd @ GO catalytic amount is only 7%; the yield of the Pd-DI @ GO catalytic No. 14 reaction is 99%, and the Pd @ GO catalytic amount is only 18%.
It is obvious from these comparative experiments that the Pd-DI @ GO has a greatly increased activity relative to Pd @ GO because the diimine ligand can play a good role in activating and protecting the active center of palladium metal; and the graphene can effectively enable reactants to be close to the active metal center due to the high electron concentration of the graphene, so that the product can rapidly leave the active metal center, the reaction rate is improved, and the yield is increased.
Application example 3
The graphene oxide supported diimine coordination palladium catalyst prepared by the method is used for catalyzing C-H activation reaction of different substrates, and the reaction can be seen in the following reaction equation:
Figure BDA0002102294210000121
wherein the reaction conditions are as follows: ArBr (1.0mmol), heterocyclic (1.2mmol), K2CO3(2.0mmol), DMAc (3.5mL), PivOH (0.5mL), 120 ℃,12 h, air atmosphere.
The results corresponding to the above equations and the resulting yield data are shown in Table 3.
TABLE 3 test of catalytic Performance of graphene oxide-supported diimine coordination Palladium catalyst for C-H activation reaction
Serial number R1 Yield (%)
1 H 97
2 4-COCH3 93
3 4-COOCH3 97
4 4-CHO 99
5 4-CF3 99
6 4-Cl 95
7 4-CH3 85
8 4-OCH3 88
9 4-CN 98
10 4-NO2 87
11 4-tert-butyl 81
12 4-Br 98
Application example 4
The graphene oxide supported diimine coordination palladium catalyst is recycled for Suzuki reaction of phenylboronic acid and p-bromobenzaldehyde by a centrifugation or filtration method, and the reaction conditions are as follows: p-bromobenzaldehyde (1.0mmol), phenylboronic acid (1.2mmol), potassium carbonate (2.0mmol), ethanol (2mL), 0.005g Pd-DI @ GO, 2h, 65 ℃, air atmosphere.
The cycle catalytic performance test of this example is shown in table 4.
TABLE 4 Cyclic catalytic Performance testing of Pd-DI @ GO catalysts
Figure BDA0002102294210000122
Figure BDA0002102294210000131
As can be seen from table 4, the catalyst of the present invention can be reused 4 times without loss of activity, showing good reusability.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. A preparation method of graphene oxide supported diimine coordination palladium is characterized by comprising the following steps: the method comprises the following steps:
1) reacting diimine with aldehyde group with a silane coupling agent to obtain a silane coupling agent modified diimine ligand;
the structure of the diimine with aldehyde group is shown as formula (1):
Figure FDA0003463191110000011
2) reacting silane coupling agent modified diimine ligand with graphene oxide to obtain graphene oxide loaded diimine ligand;
3) reacting the graphene oxide supported diimine ligand with palladium salt to obtain graphene oxide supported diimine coordination palladium;
in the step 1), the general formula of the silane coupling agent is NH2(CH2)nSi(OR1)3；
In the step 1), the structure of the silane coupling agent modified diimine ligand is shown as a formula (2):
Figure FDA0003463191110000012
in formula (2), n is 1,2, 3, 4, 5 or 6; r1is-CH3or-C2H5。
2. The preparation method of graphene oxide supported diimine coordination palladium according to claim 1, which is characterized in that: step 1) is specifically to mix diimine with aldehyde group and silane coupling agent in a molar ratio of 1: (2-5) mixing the mixture in an organic solvent, and reacting to obtain the silane coupling agent modified diimine ligand.
3. The method for preparing graphene oxide supported diimine coordination palladium according to claim 1 or 2, which is characterized in that: in the step 1), the preparation method of the diimine with aldehyde group comprises the following steps: performing halogenation reaction on the 2, 6-diisopropylaniline to obtain halogenated 2, 6-diisopropylaniline; reacting halogenated 2, 6-diisopropylaniline with glyoxal to obtain a diimine compound; reacting a diimine compound with 4-formylphenylboronic acid to obtain diimine with aldehyde groups;
the structure of the halogenated 2, 6-diisopropylaniline is shown as a formula (3):
Figure FDA0003463191110000013
the structure of the diimine compound is shown as a formula (4):
Figure FDA0003463191110000014
in the formulae (3) and (4), X represents a halogen.
4. The preparation method of graphene oxide supported diimine coordination palladium according to claim 1, which is characterized in that: the step 2) is specifically as follows: mixing a silane coupling agent modified diimine ligand and graphene oxide in a mass ratio of (1-4): 1 in an organic solvent, and reacting to obtain the graphene oxide supported diimine ligand.
5. The preparation method of graphene oxide supported diimine coordination palladium according to claim 1, which is characterized in that: the step 3) is specifically as follows: carrying out mass ratio (1-10) of a graphene oxide supported diimine ligand to palladium salt: 1, mixing the mixture in an organic solvent, and reacting to obtain the graphene oxide supported diimine coordination palladium.
6. The method for preparing graphene oxide supported diimine coordination palladium according to claim 1 or 5, which is characterized in that: in step 3), the palladium salt is selected from divalent palladium salts.
7. A graphene oxide supported diimine coordination palladium is characterized in that: is prepared by the method of any one of claims 1 to 6.
8. The use of the graphene oxide-supported diimine coordination palladium of claim 7 as a catalyst in organic synthesis reactions; the organic synthesis reaction is Suzuki reaction or C-H activation reaction.
CN201910540152.3A 2019-06-21 2019-06-21 Preparation method and application of graphene oxide supported diimine coordination palladium Active CN110302836B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910540152.3A CN110302836B (en) 2019-06-21 2019-06-21 Preparation method and application of graphene oxide supported diimine coordination palladium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910540152.3A CN110302836B (en) 2019-06-21 2019-06-21 Preparation method and application of graphene oxide supported diimine coordination palladium

Publications (2)

Publication Number Publication Date
CN110302836A CN110302836A (en) 2019-10-08
CN110302836B true CN110302836B (en) 2022-03-15

Family

ID=68077622

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910540152.3A Active CN110302836B (en) 2019-06-21 2019-06-21 Preparation method and application of graphene oxide supported diimine coordination palladium

Country Status (1)

Country Link
CN (1) CN110302836B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111072708B (en) * 2019-12-02 2022-02-22 西安近代化学研究所 graphene-Schiff base metal complex and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5852145A (en) * 1996-07-23 1998-12-22 E. I. Du Pont De Nemours And Company Polymerization processes for olefins
JP2005509701A (en) * 2001-11-16 2005-04-14 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Copolymers of olefins with vinyl silane and allyl silane
CN102500418A (en) * 2011-11-28 2012-06-20 黑龙江省科学院石油化学研究院 Magnetic bidentate imide palladium ligand catalyst and preparation method thereof
CN103447092A (en) * 2013-09-13 2013-12-18 东华理工大学 Graphene oxide supported Schiff base palladium catalyst as well as preparation method and application thereof
CN103638974A (en) * 2013-12-10 2014-03-19 中国科学院高能物理研究所 Catalyst taking graphene nano-sheet as framework as well as preparation method and application of catalyst
CN104829643A (en) * 2015-04-30 2015-08-12 河北工业大学 Alpha-diimine compound with alkyloxysilicon and application of supported metal complex of alpha-diimine compound with alkyloxysilicon

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19959251A1 (en) * 1999-12-09 2001-06-13 Basf Ag Polymerization-active transition metal complex compounds with a sterically demanding ligand system

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5852145A (en) * 1996-07-23 1998-12-22 E. I. Du Pont De Nemours And Company Polymerization processes for olefins
JP2005509701A (en) * 2001-11-16 2005-04-14 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Copolymers of olefins with vinyl silane and allyl silane
CN102500418A (en) * 2011-11-28 2012-06-20 黑龙江省科学院石油化学研究院 Magnetic bidentate imide palladium ligand catalyst and preparation method thereof
CN103447092A (en) * 2013-09-13 2013-12-18 东华理工大学 Graphene oxide supported Schiff base palladium catalyst as well as preparation method and application thereof
CN103638974A (en) * 2013-12-10 2014-03-19 中国科学院高能物理研究所 Catalyst taking graphene nano-sheet as framework as well as preparation method and application of catalyst
CN104829643A (en) * 2015-04-30 2015-08-12 河北工业大学 Alpha-diimine compound with alkyloxysilicon and application of supported metal complex of alpha-diimine compound with alkyloxysilicon

Also Published As

Publication number Publication date
CN110302836A (en) 2019-10-08

Similar Documents

Publication Publication Date Title
JP5758802B2 (en) Metal-containing organosilica catalyst, production method and use
Bhunia et al. Anchoring of palladium (II) in chemically modified mesoporous silica: an efficient heterogeneous catalyst for Suzuki cross-coupling reaction
Lai et al. Silica-supported metal acetylacetonate catalysts with a robust and flexible linker constructed by using 2-butoxy-3, 4-dihydropyrans as dual anchoring reagents and ligand donors
CN102921466B (en) Heterogeneous Au/Ze-MOF catalyst and preparation method and application thereof
CN110124718B (en) Vanadium-based single-atom catalyst for preparing phenol by directly oxidizing benzene and preparation method thereof
Bhaskar et al. Sonogashira (Cu and amine free) and Suzuki coupling in air catalyzed via nanoparticles formed in situ from Pd (ii) complexes of chalcogenated Schiff bases of 1-naphthaldehyde and their reduced forms
Zhang et al. Co–N–C supported on SiO 2: a facile, efficient catalyst for aerobic oxidation of amines to imines
CN109589978B (en) Preparation method of metal monatomic catalyst
Liu et al. Enantioselective carbonyl–ene reaction on BINOLate/titanium catalyst encapsulated in magnetic nanoreactors
Kumar et al. Efficient catalytic activation of Suzuki–Miyaura C–C coupling reactions with recyclable palladium nanoparticles tailored with sterically demanding di-n-alkyl sulfides
CN106362747B (en) A method of the catalyst and preparation method thereof for adding hydrogen to prepare phthalide for phthalic anhydride adds hydrogen to prepare phthalide with a kind of phthalic anhydride
CN110302836B (en) Preparation method and application of graphene oxide supported diimine coordination palladium
CN112221540A (en) Pd2+Loaded metal organic framework composite catalyst, preparation method and application
Cheng et al. Boosting free radical type photocatalysis over Pd/Fe-MOFs by coordination structure engineering
Dabiri et al. Pd nanoparticles supported on cubic shaped ZIF-based materials and their catalytic activates in organic reactions
CN113333021A (en) Porous polymer supported palladium catalyst with high catalytic activity and application thereof in catalyzing Suzuki-Miyaura reaction
CN102500418B (en) Preparation method of magnetic bidentate imide palladium ligand catalyst
CN110252406B (en) Catalyst for synthesizing diethyl carbonate by oxidative carbonylation of ethanol and preparation method thereof
CN111744551A (en) Application of lithium complex in hydroboration reaction of nitrile
CN104689841A (en) Synthesis and characterization of MCM loaded Pt catalyst and microwave catalytic hydrosilylation of octene
CN113117754B (en) Flower-shaped core-shell type magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst and preparation method and application thereof
Gong et al. Nitrogen-doped carbon confined cobalt nanoparticles as the steric acid-base multifunctional catalysts for Knoevenagel condensation
Fan et al. Immobilization of molybdenum-based complexes on dendrimer-functionalized graphene oxide and their catalytic activity for the epoxidation of alkenes
Shi et al. Preparation and catalytic properties of RuSalen-functionalized periodic mesoporous silicas
del Pozo et al. Homogeneous versus Supported ONN Pincer‐Type Gold and Palladium Complexes: Catalytic Activity

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant